Colloidal photonic crystals using colloidal nanoparticles and method for preparation thereof

ABSTRACT

The present invention relates to colloidal photonic crystals using colloidal nanoparticles and a method for the preparation thereof, wherein by adding a viscoelastic material into a solution containing the colloidal nanoparticles when preparing the colloidal photonic crystals, a uniform volume contraction occurs due to the elasticity of the viscoelastic material even when a nonuniform volume contraction occurs while drying a dispersion medium in the colloidal solution. Thus, it is possible to prepare 2 or 3 dimensional colloidal photonic crystals of large scale with no defects in less time.

This application is a Divisional of prior application Ser. No.11/593,052, filed Nov. 6, 2006, now U.S. Pat. No. 7,741,416 which claimsthe benefit of Korean Patent Application Nos. 10-2005-0106485 filed inKorea on Nov. 8, 2005, and 10-2006-0096866 filed in Korea on Oct. 2,2006, which are hereby incorporated by reference in their entirety as iffully set forth herein.

TECHNICAL FIELD

The present invention relates to colloidal photonic crystals usingcolloidal nanoparticles and a method for the preparation thereof, andmore particularly, to colloidal photonic crystals using colloidalnanoparticles and a method for the preparation thereof, wherein byadding a viscoelastic material, a uniform volume contraction occurs dueto the elasticity of the viscoelastic material even when a nonuniformvolume contraction occurs while drying a dispersion medium in thecolloidal solution. Thus, it is possible to prepare 2 or 3 dimensionalcolloidal photonic crystals of large scale with no defects on a surfacethereof in less time, and without a particle dimension limitation.

BACKGROUND ART

Photonic crystals are crystals having a regular structure of which thelattice distance is tens of nanometers to several micrometers, and arecapable of regulating the optical properties in a range of ultravioletrays, visible rays and infrared rays. Such photonic crystals exist inthe natural world, for example opals, butterflies, and shells etc. eachemitting beautiful light, and have been developed artificially byobserving the structure of the natural crystals and then manufactured.

Typical methods of manufacturing such photonic crystals include thetop-down method, such as photolithography and ion beam etching used in aconventional semiconductor process, and a bottom-up method usedregularly to arrange nanoparticles with a uniform dimension.

The method of manufacturing photonic crystals through the conventionalphotolithography and ion beam etching has the advantage of makingsophisticated regular structures, but has the disadvantages of very highincidental expenses and a long time being required to prepare largescale photonic crystals. On the other hand, the method of manufacturingphotonic crystals through self-assembly of nanoparticles (Korean patentlaid open 2003-0083913) has the advantages that no incidental equipmentis required and it is possible to prepare large scale photonic crystalsin less time, however it is also difficult to prepare large scalephotonic crystals with no defects. Thus, in the field of preparingphotonic crystals, a technology capable of building large scale photoniccrystals with no defects in less time through the self-assembly ofnanoparticles is an essential subject for commercial usage.

In particular, the preparation of photonic crystals using high molecularcolloidal nanoparticles has been widely studied recently, and there arevarious methods such as a deposition method by gravity [H. Miguez etal., Adv, Mater. 10,480(1998)], a vertical deposition method [P. Jianget al., Chem. Mater. 11,2132 (1999)], a vertical deposition methodthrough a temperature distribution [Y. A. Vlasov et al., Nature (London)414,289(2001), J. D. Joannopoulos, Nature (London) 414,257(2001)], andan electrophoresis method [A. L. Rogach et al., Chem Mater. 12,2721(2000)] etc.

The deposition method by gravity uses a phenomenon that, whenmotionlessly laying a solution in which a high molecular silica colloidis dispersed for a long time, particles are deposited onto the bottom bygravity and then are self-assembled. However, this method has thedisadvantages that processing time is very long and the photoniccrystals have defects. In addition, other methods are capable ofpreparing large scale photonic crystals in less time but also have aproblem in that the photonic crystals have defects.

Further, in the case of preparing 2 or 3 dimensional photonic crystalsusing the polymer colloidal particles, spherical colloidal particles aregenerally self-assembled in the structure of a face centered cubic(FCC). In this case, the particles in a colloidal solution self-assembleonto a substrate as the solution is vaporized, the colloidal particleshaving liquidity in the case that the volume ratio thereof is up to 54%,but are crystalloid with no liquidity in the case that the ratio is morethan that. Thereafter, the solution is vaporized until the volume ratioof the colloidal particles is 74%, the volume of the self-assembledcolloidal particles in the crystalloid is thus contracted [Cheng et al.,Nature (London) 410,893 (1999)]. In such a process of drying thesolution, the colloidal particles are subjected to a nonuniform volumecontraction thereby creating defects.

To solve the problem of defects resulting from such a volumecontraction, a method using a liquid metal with liquidity as a substratecomponent may be used, but there is a problem in that it is difficult toapply commercially [Griesebock et al., Chem mater., 14,4023 (2002)].

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide colloidal photoniccrystals using colloidal nanoparticles, a method for the preparationthereof and a method for preparing a colloidal photonic crystal baseusing the photonic crystals, whereby a uniform volume contraction occursdue to the elasticity of the viscoelastic material even though anonuniform volume contraction occurs when drying a dispersion medium ina colloidal solution. Thus, it is possible to prepare 2 or 3 dimensionalcolloidal photonic crystals of large scale with no surface defects inless time and without a particle dimension limitation.

Another object of the present invention is to provide colloidal photoniccrystals using colloidal nanoparticles, a method for the preparationthereof, and a method for preparing a colloidal photonic crystal baseusing the photonic crystals, which are suitable for use in lasers,sensors, piezo-electric sensors, actuators, chromatography separationmembranes, catalyst carriers, optical integrated circuits, opticalfilters, liquid crystal alignment layers, super hydrophilic or superwater-repellent membranes, photomasks, antireflection films, and displaydevices etc. which all require photonic crystals.

To achieve the above objects, the present invention provides a methodfor the preparation of colloidal photonic crystals using colloidalnanoparticles comprising a step of adding a viscoelastic material into asolution containing the colloidal nanoparticles.

The present invention also provides colloidal crystals which compriseself-assembled nanoparticles and a viscoelastic material settling thenanoparticles to have a predetermined elasticity.

Further, the present invention provides a method for the preparation ofa colloidal photonic crystal base comprising a step of self-assemblinganother layer of colloidal particles, semiconductor particles, metalparticles or metal-oxide particles into the gaps of the colloidalphotonic crystal particles prepared by the above method.

Further, the present invention provides a method of preparing acolloidal photonic crystal base comprising the steps of producing areverse cast using the colloidal photonic crystals prepared by the abovemethod; and transcribing the structure and shape of the reverse castinto a base.

The present invention is described in detail hereinafter.

The present inventors confirmed that, as a result of drying afterdissolving an added viscoelastic material into a dispersion medium of asolution containing colloidal nanoparticles, a uniform volumecontraction occurs due to the elasticity of the viscoelastic materialwhen drying, such that colloidal photonic crystals with no defects canbe prepared therefrom, and thus accomplishing the object of the presentinvention.

The colloidal photonic crystals according to the present invention arecharacterized in that they are prepared by vaporizing a dispersionmedium from a solution to self-assemble the colloidal nanoparticles ontoa substrate after adding a viscoelastic material into the solutioncontaining the colloidal nanoparticles.

The viscoelastic material used in the present invention makes a uniformvolume contraction occur during the drying of the dispersion medium ofthe colloidal solution, thereby preventing the resulting colloidalphotonic crystals from having defects.

There is no limitation on the viscoelastic material as long as it hasnormal viscoelasticity, however it is preferable to use a compounddissoluble in the dispersion medium of the solution containing thecolloidal nanoparticles.

Specifically, in the case that the solution into which the viscoelasticmaterial is added is a solution of water dispersed colloidalnanoparticles, every material capable of showing viscoelasticity whendissolved in an aqueous solution can be used, particularly polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, poly(p-phenylenevinylene), polyethylene glycol, polyethyleneamine, or dextrine etc., andin the case that the solution into which the viscoelastic material isadded is a solution of colloidal nanoparticles dispersed in an organicsolvent, every material capable of showing viscoelasticity whendissolved in an organic solvent can be used, particularly polystyrene,polymethylmethacrylate, polyacrylate, or polyvinyl chloride etc.

The weight-average molecular weight (Mw) of the viscoelastic material ispreferably 10 to 1,000,000.

The above viscoelastic material is preferably contained at 0.04 to 1 phrfor 100 phr of nanoparticles in the colloidal nanoparticle solution. Itis difficult to manufacture colloidal crystals with no defects when theviscoelastic material content is less than 0.04 phr, and theviscoelastic material prevents the colloidal particles fromself-assembling, thereby inhibiting colloidal crystals from forming,when the amount of the viscoelastic material is more than 1 phr.

The above viscoelastic material is added to the solution containing thecolloidal nanoparticles, which then self-assemble onto a substrate asthe dispersion medium is vaporized from the solution, whereby colloidalphotonic crystals can be obtained.

Specifically, the colloidal photonic crystals of the present inventioncan be prepared by the following steps of evenly dispersingnanoparticles into a dispersion medium; dissolving an added aviscoelastic material into the solution; vaporizing the dispersionmedium from the solution to self-assemble the particles on an interfaceof a dispersion medium-air-substrate; and continuously transferring theself-assembled particles onto the interface.

There is no limitation on the nanoparticles, it can be selected from agroup consisting of a polymer of polystyrene, polyalphamethylstyrene,polyacrylate, polymethylmetacrylates, polybenzylmetacrylate,polyphenylmetacrylate, poly-1-methylcyclohexylmetacrylate,polycyclohexylmetacrylate, polychlorobenzylmetacrylate,poly-1-phenylethylmetacrylate, poly-1,2-diphenylethylmetacrylate,polydiphenymethylmetacrylate, polyfurfurylmetacrylate,poly-1-phenylcyclohexylmetacrylate, polypentachlorophenylmetacrylate,polypentabromophenylmetacrylate, polydimethylsiloxane orpoly-N-isopropylacrylamide etc., and copolymers thereof.

Particularly, the nanoparticles may be a metal oxide such as titaniumoxide, zinc oxide, cerium oxide, tin oxide, thallium oxide, bariumtitanite, aluminum oxide, yttrium oxide, zirconium oxide, or copperoxide etc. Further, the nanoparticles may be a metal such as bismuth(Bi), lead (Pb), selenium (Se), or antimony (Sb) etc.

The nanoparticles are preferably 0.1 to 10 μM in diameter. It isdifficult for the nanoparticles to self-assemble by vaporization of thedispersion medium if the diameter of the nanoparticles is less than 0.1μm, and preparation of uniform photonic crystals is difficult if thediameter of the nanoparticles is more than 10 μm, as the particles sinkeasily or movement of the particles is not facilitated by vaporizationof the dispersion medium.

It is desirable to select the dispersion medium from materials which donot dissolve the nanoparticles, Specifically, the dispersion medium maybe selected from a group consisting of water, methanol, ethanol,propanol, butanol, ethylene glycol, glycerol, perfluorodecalin,perfluoromethyldecalin, perfluorononane, perfluoro iso acid,perfluorocyclohexane, perfluoro1,2-dimethylcyclohexane,perfluoro-2-methyl-2-pentene, perfluorokersene, hexane, cyclohexane,toluene, xylene, styrene, methylmethacrylate, and chloroform etc.

Vaporization of the dispersion medium is conventionally required to becarried out below the boiling point of the dispersion medium. The fasterthe vaporizing speed of the dispersion medium is, the less time thatphotonic crystals are self-assembled onto the interface of thedispersion medium-air-substrate. There is a problem that photoniccrystals' defects may be induced if the vaporizing speed is too fast andregular photonic crystals cannot be obtained if the vaporizing speed istoo slow. In the present invention, the optimum vaporizing condition forforming the crystals is varied in accordance with the kind of dispersionmedium, and a person skilled in the art may easily select the conditionfrom the disclosure of the present invention, therefore it is notnecessary to specifically describe such a condition.

The photonic crystals formed on the interface of the dispersionmedium-air-substrate through the above self-assembling process arecontinuously transferred onto the substrate, and the photonic crystalsare moved by continuously moving the substrate or by continuouslyvaporizing the dispersion medium while the substrate is inserted in thedispersion medium perpendicularly or with an inclination of apredetermined angle.

FIG. 1 is a schematic diagram explaining the principal of preparing thecolloidal photonic crystals with no defects according to the presentinvention compared to a conventional method of preparing colloidalphotonic crystals.

Referring to (a) in FIG. 1, nanoparticles (10) are self-assembled on abase (12) as a crystalloid form by a dispersion medium (11) is vaporizedin a colloidal solution. A defect (13) forms due to a nonuniform volumecontraction in the process of drying the dispersion medium (11), therebyforming colloidal photonic crystals with defects.

On the contrary, referring to (b), in the case of using a dispersionmedium 15 with a viscoelastic material dissolved in the colloidalsolution, a uniform volume contraction occurs due to the elasticity ofthe viscoelastic material 15, even if a nonuniform volume contractionoccurs in the process of drying the dispersion medium, thereby formingcolloidal photonic crystals with no defects.

The colloidal photonic crystals self-assembled according to the presentinvention may be further subjected to a step of filling gaps in thephotonic crystals with a semiconductor, metal, metal oxide, or organicmatter etc.

The semiconductor can be selected from a group consisting of commonlyused semiconductors such as Si, CdS, CdSe, and GaAs etc.; the metal canbe selected from a group consisting of commonly used metals such as Ag,Au, Al, Pt, Pd etc., and alloys thereof; the metal oxide can be selectedfrom a group consisting of common metal oxides such as AlO₂, TiO₂, SiO₂,ZrO₂, Fe₂O₃, and ZnO etc.; and the organic matter can be selected from agroup consisting of polydimethylsiloxane, polythiophene, polyquinoline,polypyrrole, polyacetylene, polyprolene, Poly(p-phenylene vinylene)etc., or derivatives thereof.

The present invention also provides colloidal photonic crystalscomprising self-assembled nanoparticles and a viscoelastic materialsettling the nanoparticles with a predetermined elasticity.

Further, the present invention provides a colloidal photonic crystalbase and a method for the preparation thereof, comprising a step ofself-assembling another layer of colloidal photonic particles,semiconductor particles, metal particles or metal-oxide particles intogaps of the colloidal photonic particles prepared by the above method.

Further, the present invention provides a method of preparing acolloidal photonic crystal base comprising the steps of manufacturing areverse cast using the colloidal photonic crystals prepared by the abovemethod as a cast; and transcribing a structure and shape of the reversecast into a base.

The colloidal photonic crystals and colloidal base of the presentinvention prepared as described above are adapted to be used inmanufacturing lasers, sensors, piezo-electric sensors, actuators,chromatography separation membranes, catalyst carriers, opticalintegrated circuits, liquid crystal alignment layers, super hydrophilicor super water-repellent membranes, photomasks, antireflection films,and display devices etc. requiring the photonic crystals.

BRIEF DESCRIPTION OF THE DRAWINGS

The above aspects and features of the present invention will be moreapparent by describing certain embodiments of the present invention withreference to the accompanying drawings, in which:

FIG. 1 is a schematic diagram explaining the principal of preparingcolloidal photonic crystals with no defects according to the presentinvention compared to conventional preparation of colloidal photoniccrystals;

FIG. 2 and FIG. 3 are photographs by scanning electron microscope eachshowing colloidal photonic crystals prepared according to one embodimentof the present invention;

FIG. 4 is a graph showing the intensity along a wavelength of reflectedlight in accordance with the reflection angle of the colloidal photoniccrystals prepared according to one embodiment of the present invention;

FIG. 5 and FIG. 6 are photographs by scanning electron microscope eacheach showing a reverse structure and a transcribed structure ofcolloidal photonic crystals prepared according to one embodiment of thepresent invention; and

FIG. 7 is a photograph by scanning electron microscope showing colloidalphotonic crystals prepared according to a comparative example.

-   -   10: nanoparticles    -   11: dispersion medium including viscoelastic material    -   12: base 13: defect    -   14: dispersion medium not including viscoelastic material    -   15: viscoelastic material

BEST MODES FOR CARRYING OUT THE INVENTION

Practical and presently preferred embodiments of the present inventionare illustrated as shown in the following examples.

However, it will be appreciated that those skilled in the art, onconsideration of this disclosure, may make modifications andimprovements within the spirit and scope of the present invention.

EXAMPLE Example 1

In a colloidal nanoparticle solution, water was used as a dispersionmedium and 460 nm diameter polystyrene spherical particles were used asnanoparticles.

The 460 nm diameter polystyrene particles were dispersed in the water at0.5 weight percent, and then 0.21 weight percent of polyvinylpyrrolidone, as a viscoelastic material, was dissolved in the colloidalnanoparticle solution. After a substrate was deposited in the solution,the dispersion medium was vaporized in an oven at 60° C., wherebycolloidal photonic crystals were prepared.

This was confirmed through observation with a scanning electronmicroscope as shown in FIG. 2.

Example 2

Photonic crystals were obtained by the same method as example 1 with theexception that 0.63 weight percent of polyvinyl pyrrolidone was used asthe viscoelastic material. This was confirmed through observation with ascanning electron microscope as shown in FIG. 3.

Example 3

Photonic crystals were obtained by the same method as example 1 with theexception that 0.63 weight percent of polyacrylic acid was used as theviscoelastic material.

Example 4

Photonic crystals were obtained by the same method as example 1 with theexception that 0.63 weight percent of polyvinyl alcohol was used as theviscoelastic material.

Example 5

Photonic crystals were obtained by the same method as example 2 with theexception that 180 nm diameter polystyrene was used as the nanoparticle.

Example 6

Photonic crystals were obtained by the same method as example 2 with theexception that 240 nm diameter polystyrene was used as the nanoparticle.

Using the photonic crystals prepared in example 6, the intensity oflight radiated in the direction perpendicular to the photonic crystalsand in accordance with the direction of reflected light was measured,and the results are shown in FIG. 4. As shown in FIG. 4, photoniccrystals varying the wavelength of reflected light in accordance withdirection are suitable for use as an optical filter.

Example 7

Photonic crystals were obtained by the same method as example 2 with theexception that 1 μm diameter polystyrene was used as the nanoparticleinstead of 460 nm diameter polystyrene particles.

Example 8

Polydimethylsiloxane rubber and a hardener were inserted into thecolloidal photonic crystals prepared in example 2 at a weight ratio of10:1, and then were hardened at 60° C. Thereafter, a cast with a reversestructure of the colloidal photonic crystals was prepared by detachingthe polydimethylsiloxane rubber from the colloidal photonic crystals(FIG. 5).

The cast of the polydimethylsiloxane rubber with the reverse structureof the colloidal photonic crystals was pressed onto a film coated withpolystyrene, heat treated at 150° C. for 10 minutes, and then cooled atroom temperature. Thereafter, the cast of the polydimethylsiloxanerubber was detached from the polystyrene film and the reverse structureof the rubber cast was transcribed into the film (FIG. 6).

Comparative Example 8

Photonic crystals were obtained by the same method as example 1 with theexception that the viscoelastic material was not used.

The result was observed with a scanning electron microscope as shown inFIG. 7.

INDUSTRIAL APPLICABILITY

According to the present invention, a uniform volume contraction occursdue to the elasticity of the viscoelastic material even when anonuniform volume contraction occurs while drying the dispersion mediumin the colloidal solution. Thus, it is possible to prepare 2 or 3dimensional colloidal photonic crystals of large scale with no defectson a surface thereof in less time, and without a particle dimensionlimitation. they are suitable for use in lasers, sensors, piezo-electricsensors, actuators, chromatography separation membranes, catalystcarriers, optical integrated circuits, liquid crystal alignment layers,super hydrophilic or super water-repellent membranes, photomasks,antireflection films, and display devices etc. requiring the photoniccrystals.

Those skilled in the art will appreciate that the conceptions andspecific embodiments disclosed in the foregoing description may bereadily utilized as a basis for modifying or designing other embodimentsfor carrying out the same purposes of the present invention. Thoseskilled in the art will also appreciate that such equivalent embodimentsdo not depart from the spirit and scope of the invention as set forth inthe appended claims.

1. Method of preparing colloidal photonic crystals, comprising thefollowing steps of: a) dispersing nanoparticles evenly in a dispersionmedium to form a solution; b) dissolving a viscoelastic material intothe solution; c) vaporizing the dispersion medium from the solution toself-assemble the nanoparticles on an interface of a dispersionmedium-air-substrate; and d) transferring the self-assembled particlesonto the substrate, wherein the viscoelastic material is one or moreselected from the group consisting of polyvinyl pyrrolidone, polyvinylalcohol, poly(p-phenylene vinylene), polyethylene glycol,polyethyleneamine, dextrine, polymethylmethacrylate, polyacrylate andpolyvinyl chloride.
 2. The method of preparing colloidal photoniccrystals as set forth in claim 1, wherein the weight-average molecularweight (Mw) of the viscoelastic material is 10 to 1,000,000.
 3. Themethod of preparing colloidal photonic crystals as set forth in claim 1,wherein the viscoelastic material is contained by 0.04 to 1 phr for 100phr of the nanoparticles in the colloidal nanoparticle solution.
 4. Themethod of preparing colloidal photonic crystals as set forth in claim 1,wherein the nanoparticle is one or more selected from the groupconsisting of polystyrene, polyalphamethylstyrene, polyacrylate,polymethylmetacrylates, polybenzylmetacrylate, polyphenylmetacrylate,poly-1-methylcyclohexylmetacrylate, polycyclohexylmetacrylate,polychlorobenzylmetacrylate, poly-1-phenylethylmetacrylate,poly-1,2-diphenylethylmetacrylate, polydiphenymethylmetacrylate,polyfurfurylmetacrylate, poly-1-phenylcyclohexylmetacrylate,polypentachlorophenylmetacrylate, polypentabromophenylmetacrylate,polydimethylsiloxane and poly-N-isopropylacrylamide.
 5. The method ofpreparing colloidal photonic crystals as set forth in claim 1, whereinthe nanoparticle is one or more selected from the group consisting oftitanium oxide, zinc oxide, cerium oxide, tin oxide, thallium oxide,barium titanite, aluminum oxide, yttrium oxide, zirconium oxide, andcopper oxide.
 6. The method of preparing colloidal photonic crystals asset forth in claim 1, wherein the nanoparticle is one or more selectedfrom the group consisting of bismuth (Bi), lead (Pb), selenium (Se), andantimony (Sb).
 7. The method of preparing colloidal photonic crystals asset forth in claim 1, wherein the diameter of the nanoparticle is 0.1 to10 μm.
 8. The method of preparing colloidal photonic crystals as setforth in claim 1, wherein the dispersion medium is one or more selectedfrom the group consisting of water, methanol, ethanol, propanol,butanol, ethylene glycol, glycerol, perfluorodecalin,perfluoromethyldecalin, perfluorononane, perfluoro iso acid,perfluorocyclohexane, perfluoro-1,2-dimethylcyclohexane,perfluoro-2-methyl-2-pentene and perfluorokersene.
 9. The method ofpreparing colloidal photonic crystals as set forth in claim 1, furthercomprising a step of filling gaps in the colloidal photonic crystalswith a semiconductor, metal, metal oxide, or organic matter.
 10. Themethod of preparing colloidal photonic crystals as set forth in claim 9,wherein the semiconductor is one or more selected from the groupconsisting of Si, CdS, CdSe and GaAs; the metal is one or more selectedfrom the group consisting of Ag, Au, Al, Pt and Pd; the metal oxide isone or more selected from the group consisting of AlO₂, TiO₂, SiO₂,ZrO₂, Fe₂O₃, and ZnO; and the organic matter is one or more selectedfrom the group consisting of polydimethylsiloxane, polythiophene,polyquinoline, polypyrrole, polyacetylene, polyprolene, Poly(p-phenylenevinylene) and derivatives thereof.